Method of producing so



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METHOD 0F PRODUCING sog ATTORNEYS F. w. DE JAHN 1-.r Al.

METHOD OF PRODUCI'NG SO2 I Feb. 26, 1935. l

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ATTORNEYS Patented Feb. 26, 19354 UNITED STATES METHOD F PRoDUoING soz Fredik W. ae Jahn and Jacob D. Jenssen,

l New York, N. Y.

Application September 16, 1931, Serial No. 563,025

12 Claims. (Cl. .Z3- 480) This invention relates to the production of SO2 in such manner as to enable it to be recovered in the form of 100%, SO2, and the object of the invention is to accomplish said end by appropri- 5 ate economic and relatively inexpensive .apparatus and procedure.

Gases containing SO2 are ordinarily generated byburning sulphur or sulphur-bearing ores with air. When sulphur (brimstone) is burned, a gas containing 15% to 17% SO2 is obtained, while when sulphur-bearing ores are burned, gases containing irom`6% to 11% SO2 are obtained. According to existing practice, 100% SO2 can be obtained by cooling and scrubbing SO2 containing i5 gases with Water which dissolves the SO2, and the solution of SO2 in water is then heated to drive out the SO2 Which is then liqueiiable at atmospheric temperatures at a pressure of` about 100 pounds Vper square inch. This process requires `large quantities of water and fuel and is correspondingly costly. `The reason Why large quantitiesoi" water are necessary is that the solubility of SO2 in water is not very high and depends on the percentageof SO2 in the gases and the temperature of the water used for absorption. For example, a gas containing 15% SO2 will produce a solution in water at a temperature of 68 F. which contains 1.7% SO2 by weight.- A gas containing l 10% SO2 will produce a 1.1% solution and a gas of 6% SO2 will only produce a .67% solution. In other Words evenv if the SO2 is generated by burning sulphur yielding the maximum strength of SO2 in the gas, large quantities of water are needed for absorption with consequent correspondinglylarge expenditure of heatand for equipment for-the removal of the SO2 from the large volumeof solution, and in-"a case of gases containing from 6% to 8% SO2 which are representative of most slnelter gases, the solubility of 40 the SO2 is so small as to make the recovery of 100% SO2 altogether too costly.

We have now devised a method of concentrating the SO2 gas in a manner so simple, eflicient, and inexpensive, that 100% SO2 can be obtained 'at a cost of production which makesthe use of SO2 possible in industries where its cost up to the present has been prohibitive.

The invention is illustrated in the accompanying `drawings which represent diagrammaticallyV 5 0 the method of procedure and the apparatus required, Fig. 1 showing one course of procedure and Fig.' 2 a modifiedform, and Fig. 3 is a modined detail of Fig. 2.

The process 4Vand apparatus of Fig. 1

60 wasteproduct into which consequently no element of cost enters and where a savingV even may` tween 1200 to 1800" F. The tower is fed throughV the inlet 18 with a water solution of SO2 from the absorber 2. The gases'leave the tower 1 through the outlet 13 and pass into the bottom of the absorber 2through the line 13a, 13b, and 14. Sufcientwater `is introduced into the absorber 2 through its upper inlet 15 'to absorb all of the SO2 in the gases, said gases freed from SO2 then leaving the absorber 2 through the outlet 16 past valve 27 to the stack. The amount oi water depends on the temperature and percentage of VSO2 inthe gas. The solution of SO2 in water leaves the absorber 2 through the outlet 17 and passes throughV the line 17a .into the tower 1 through the 'inlet l8.f In the tower 1 the solution coolstlie hot rgases entering at 12 and is itselfl heated up so as to give up' the dissolved SO2. Inasmuch, however, as the amount of water'needed for absorbing the SO2 in the absorber 2 exceeds the amount needed to cool the hot gases to water temperature, only a part of the dissolved SO2 is driven out in Ytower 1. As it is an object of 'the invention to free the solution fromV SO2 as cornpletely as possible, the solution whichleaves the tower 1 through the,` outlet 19 is passed'through a heat-exchanger 4, then through the heater 5, where it is heated up to about 200 F., preferably by means of steam. The not liquid nextenters the separator 6 where the SO2 gas is separated from the hot water. The SO2 gas from the separator 6 is cooled in the reiiux cooler 3 and enters the `pipe 13a Vthrough which ,the gases from the tower 1 ow on their'way to the absorber 2, thereby increasing the percentage of SO2 in the gases entering the absorber 2. inasmuch as the solubility of SOzin water is directlyproportional to the percentage of SO2 in the gases, the' same amount of water constantly introduced into the absorber 2 will absorb just as completely 20 pounds of SO2 with 20%V SO2 in Vthe gas as l'pounds of SO2 with 10% SO2 in the gas, the result being that the SO2 solution, leaving the absorber 2, Will gradually contain a higher percentage or" dissolved SO2, which, Ybeing introduced into the tower 1, will gradually increase the percentage of SO2 in the gas leaving the tower 1' (with or without additional VSO2 from the separator 6) which in lturn will increase the percentage of SO2 in the solutionfro'm the absorber' 2. For example, if 100 pounds `SOzper hour in the form of hot 10% gas is introduced at lpoint 12 into the tower 1, this will all be absorbed in the absorber 2 and returned to the tower 1. After an hour the gas leaving the tower will contain 20y Volumes of SO2 and 90 volumes inertgases or 18.18% SO2 by volume. After two hours, the gasY leaving tower 1 will contain 30 volumes of SO2 and 90 volumes inert gases or 25% SO2 by volume. After eight hours the gas leaving tower 1 will contain 90 volumes of SO2 and 90 volumes of inert gases or 50% SO2, 'and therefore, at the end of eight hours, the solution leaving the absorber 2 will contain 5.50% SO2 by weight instead of 1.1% SO2 by weight as at the beginning of the run with 10% SO2 in the hot gases entering the tower 1. If, therefore, after eight hours (still continuing the example) one-fth of the solution is constantly withdrawn through regulating valve 11 and heated up to 200 F. by passage through the reilux cooler 3, heat-exchangers 7 and 8 and heater 9, the total amount, 100 pounds SO2 per hour (entering tower 1), is recovered as 100% SO2 at a cost whichrepresents but one-fifth of the expense which would be required to produce 100 SO2 by previously known methods. The hot water which leaves the separator 6 is passed through the heat-exchanger 4 by means of the pump 20 and gives up approximately 77% of its heat to the SO2 solution flowing through the heat-exchanger 4. The remaining heat of this water is utilized to preheat in the heat-exchanger 7 the SO2 solution which flows from the reflux cooler 3 into the heat-exchanger 7. After passing through the heat-exchanger 7, this water is run to wasteas indicated at W, or Aif shortage of pressure of `14.7 points above atmospheric.

water exists, then into a cooling tower from whence it may be pumped to the top of the absorber 2.

The preheated SO2 solution from the heat-exchanger 7 is passed through the heat-exchanger 8 where it is preheated by hot water from the heater 9. From the heater 9 the hot SO2 solution Y enters the separator 10, where the SO2l gas 40` is separated from the hot water, the SO2 gas have ing been freed from water vapor in drying tower T by scrubbing with Vstrong sulphuric acid (preferably 91% to 93%) The dried SOzgas is then compressed at C to approximately 100 pounds pressure, cooled, liquefied, and stored or shipped.

The hot water from the'separator 10 is pumped by the pump 30 through the heat-exchanger 8, counter-current with respect to the SO2 solution l passing through theV heat-exchanger 8 and ultimately passes to waste at W2 or is dealt with in the same manner as the water flowing out Vat W.

if strong solutions of SO2 in water are desired,

the ventilator 21 may discharge the gasesinto a compressor 22, in which case valve 24 is closed and valves 25 and 26 are opened. The compressor 22 compresses the gas to a minimum of 14.7 pounds above atmospheric and the SO2 in the compressed gas is absorbed under this pres'- surein the absorber 2, valves 11, 23, and 27 being partly closed and thereby serving to maintain pressure in the absorber 2.

The solubility of SO2 increases proportionately with the pressure and is therefore double at a BJ this means with the gases containing 50% SO2 at the inlet of the compressor, the compressed gas will be equal to 100% SO2 in relation to the water, and the maximum strength or" SO2 solution'is therefore obtained.

In cases Where the water entering the absorber 2 is excessively cool (as in winter or for other reasons) and the hot gases entering the tower 1 are of medium temperature, say 10001200 F., it is not necessary to return the SO2 from the separator 6 through reflux cooler 3 and back into the line 13a. In such cases the valve 32 is closed, valve 34 opened, and a fan 31 in the connection 33 shown in dotted lines leads any SO2 from the separator 6 directly into the 100% SO2 line 'leading from the separator 10 to the drying tower T.

In a typical operation of the system as thus far described, the strength of the SO2 solution in operation. 1n some cases the SO2 solution in theY Y absorber 2 may be maintained at 67% or other percentages. Whatever the degree of solution to be maintained may be, however, it will be in excess of 1% for practical purposes. Y

Process'omd apparatus of Fig.V 2*

In Fig. 2 a modification of the invention is depicted which has considerable advantages over the layout shown in Fig. 1. The two igures'Y have in common the source of SO2-bearing. gases O, the gas inlet 12, the scrubbing and cooling tower 1, the gas outlet 13, the fan 21,the gas inletline 14, the absorber 2, the Water inlet 15', the gas outlet to the stack 16, the solution outlet'l'l fromV the absorber 2 and the branched connection 17a' with its liquid inlet 18 into tower l, the other` branch being under the control of regulating valve 11. In Fig. 2, however, the solution which passes valve 11, takes a different coursev from that shown in Fig. 1. From 1l in 2 the solution passes through line 40 into the heat-exchanger 41, in which the temperature of the solution is raised to say Y F. The solution thereupon' at said temperature passes through the separator 10 and the liquid part is returned through line 42 and pump 43 into the tower A1 at a point suiciently high to increase'the temperature of the hot liquid flowing in through the line 42 plus the cold liquid' flowing in at 18 to say while leaving sufficient room above to enable the inflowing cold solution at 18 to cool the gases of the tower 1 to approximately the temperature of the solution flowing in at 18. *The amount of solution flowing in at 18 is regulated through valve 23 to accomplish the said purpose of obtaining approximately equal temperature of the inilowing solution and the outfiowing gas.

The SO2 gas which is separated from the hotwater in the separator 10 is used in part for reintroduction into tower 1 through line 44, strengthening the SO2 content of the gas leaving the tower l. The balance of lthe gas is withdrawn through line 45, past the indicator 46 into the drier T and then to the compressor C. The indicator 46 enables the operator to apply such'coni trol tothe system as will maintain the withdraw-V al of the 'final'SOz product at C at the same rate as SO2 enters the tower 1 through inlet 12.

In some cases 'it is advisable to maintain the iinal separator 10 Linder partial vacuum so as, to facilitate the removal of the right amount of SO2 from the solution without being obliged to heat the solution up too high before running it to the scrubbing and cooling tower l.V This would apply for example, in case the SO2 in the gas enter# ing the cooling tower at l2 is 6% or less and the cooling water entering the absorber 2is 70% or higher.

In Fig. 2 legends have been applied to illustrate the temperature conditions and the quantities of Water and SO2 at different parts of the system. These legends are, of course, illustra-v tive merely. They show, however, that the systeni, once it is in complete operation, is thermally self-sustaining, not requiring, as in the case of Fig. l, the useof any steam or heat from outside sources. This, of course, is of great importance from an economical standpoint.

When the apparatus shown in Fig. 2 is started up, the whole of the solution passing through the line 40 is not introduced into the heat exchanger 41, but the major part of the solution is removed at W3 and either flows to waste or is used as indicated in connection Vwith the liquid outlets W, W2 of Fig. l. `That part of the solution running through line 40 which enters theI heat interchanger'41, is heated up by the hot liquid flowing through `the line 19 and as the heat gradually builds up and' is returned into the tower l through the'line 42, more and more of the solution is allowed to pass from theline 40 into the heat exchanger 41 and finally when the apparatus is fully functioning, the valve 47 is closed and no water leaves the system at all except through the outlet W4. In the meantime, as more of the solution passes through the heat interchanger 41, less `of the solution passes throughline 17a into the tower 1. The temperature in the lower part of thetower 1 is such that the liquid leaving at 19 is free from SO2 so that there is no loss of SO2` at the outlet W4 and there is no requirement at this point, as in the case of Fig. 1, for using any heater such as 5, separator *6,` pump 20, reflux cooler 3 or a subsequent heate129.

It will be seen that the system illustrated in Fig. l supplies practically all but avery small part of the heat needed for the entire operation, only a relatively small amount of specially created heat being required for the heaters 5 and 9 andY for the operation; of the pumps, fans, and compressor. In the case of Fig. l the pumps, fans, and compressors are preferably steam-driven, and the exhaust steam which is still suiciently hot for the work required in the heaters 5 and 9 (in view of the heat economy of the system asa whole) are used for the saidheatersjV In Fig. 2, the system itself supplies all` the heat which is needed for the entire operation of the system as such, so that the pumps, fans,and compressors can all be driven by electric, hydraulic, or other forces, including, of course, steam, if economically available.

It is to be understood that all figures heretofore given in this specification and in the drawings are illustrative merely.

In the case of the present invention it will be seen that the apparatus is relatively simplaso that the cost of installation and maintenance is small, while performance is continuous, requiring very little supervision. The hot SO2 gases from the smelters, being waste gases, are cost-free, and the only element of cost involved in the entire process lies in obtaining an adequate water supply and the cost of the small amount of power which is necessary to drivel the pumps, the com-` i pressors, andthe fans, and (in the case of Fig. l) to supplement the heat which accumulates in the apparatus andis required forthe final extraction of Soz'from the water solution.

The foregoing `invention is of particular'value as a means for utilizing the waste and troublesome SO2 gases from smelters and for rendering available the lSO2 recovered bythe use of the process for industries such as the sulphite pulp industry which Ydesire asource of supply of 100% SOzrbut` have no source for this material except atv costs which are prohibitive fortheir particular situation. Y

Inasmuch as the product of the process is 100% SO2, it can be usedv eiectively and conveniently inthe manufacture of sulphuric acid in localities where local manufacture of S03 by the contact-method or the like would be protable, but Where itis desirable to avoid the capi-` ent practice of purifyingthe gases now utilized i in all existing Contact sulphuric acid plants that it would be profitable to reform the conduct of the contact sulphuric acid `process so as to have it begin with theY preparation of,l00% SO2 in accordance with the methods described in this .application, thenniixing the 100% SO2 `thus 'obtained with air in theproper proportions for conversion into sulphuric anhydride and then passing the mixture thus obtained over a catalyst capable of supportingthe reactionby which SO2 plus oxygen are converted into S03. Both as to cost of plant aswell ascost ofoperation the new method of Vmaking sulphuric acid represents a distinct and important advanceover anyV known methods. The process can also Vbe usefully employed where Soz'is desired for metallurgical operations in a locality nearwhich there is an available supply of sulphur pyrites or sulphurbearing material. p V i InFig. -3ofthe drawings the hot solution in the heater 41 of Fig. 2 is shown'as being led through a heater 48 in the hot gas line extending from 0 to l2, where it receives indirect heat and then discharges at a temperature suiciently highl to assure the liberation of ally absorbed VSO2 into the separator 10. 'I'he hot water from separator l0 is now not onlyfree -iroin absorbed SO2, but sufficiently hot to b e available las a part of the the heating medium flowing through 4l and is consequently discharged into the hot water line 1,9, whilel only suchpart Aof this hot water as may be necessary for washing the gases in the tower 1 is returned directly to the tower 1.

We claim:

1. The process which comprises establishing a supply of hot SO2-bearing gas, the SOZ'content of which is less than 50%, leading such hot gas into direct contact with a cool aqueous medium containing SO2 in solution and thereby releasing SO2 from the solution, absorbing the gaseous SO2 in said step in water and introducing the Whole of the solution thus formed into the hot SO2- bearing gas until. equilibrium is established in the solution and the SO2 liberated from the solution plus the SO2 of the hot gases reach a percentage which approximates the capacity of SO2 absorption of cool water at the prevailing temperature and pressure, then bringing the gases resulting from the contact of the hot SO2 bearing vgases and the SO2 solution first mentionedl into the hot SO2 gas, is separated from any SO2 still contained therein andsuch SO2 is recovered as a part of lthe ultimate SO2 product of the entire A process. v

3. A process such as set forth in claim 41 in Y which the aqueous medium, after Contact with the hot SO2 gas, is separated from any SO2 still contained therein and-such SO2 is recovered as a part of the ultimate SO2 product of the entire process, the heat contained in the vaqueous medium after such separation being employed. as a i'neansV for elevating the temperature of the SO2 Y solution in the'nal step wherein the Vultimate SO2 product yis separated from that part of the strong SO2 solution which is not used as the aqueous'medium to cool and enrich the hot gases `mate SO2 product of the process is collected as product. Y

5. A process such as described in claim 1 in whichl the gases resulting from contact between the 'not SO2 gases and the aqueous medium are compressed prior to being brought into absorbing contact with the cool water. Y GJA process such as set forth in claim 1 in which water separated from SO2 in the ultimate stage of the process where SO2 is recovered as product, isreturned as cool water to the cool water supply used to absorb SO2 from the gas mixture which results from contact between the hot SO2-bearing gases and the aqueousmedium. 7. A process as set forth in claim 1 inV which temperature conditions are maintained at that stage of the process where the hot SO2-bearing gas comes into contact With the aqueous medium that said aqueous medium, uponV discharge from said stage, shall be substantially free from SO2. 8. 1A process as set forth in claim 1 in which temperature conditions are maintained at that stage of the process where the hot SO2-bearing gas cornes into contact with the aqueous medium that said aqueous medium, upon discharge from said stage, will contain suicient heat to effect,

under heat-exchange conditions, effective sep-Y aration of SO2 from that part of the rich SO2 solution which is employed forY the recovery of the ultimate SO2 product of the process as whole. y

9. A process such as set forth in claimA 1 in which the hot aqueous residue from the Vfinal separation of SO2 from the solution is returned under retention of its heat to the initial stage of the process for contact with a fresh supply of hot SO2 gases. f

10. A process such as set forth in claim 1, in which the SO2 separated from the solution at the endof the process is divided, one portion being withdrawn, dried, and compressed as final product while the other portion is introduced into the gas stream inthe region where it comes into direct contactwith the cool aqueous solution rich in SO2.,Y

11. The process as set forth in claim 1 in which such a relation of temperatures in the several parts ofthe system is maintained that the entire process is thermally independent of v exterior sources of heat other than those involved in establishing the supply of the hot SO2-bearing gas, said maintenance includingafter the establishment of the equilibrium set forth, a constant inflow at relatively constant high temperature SO2-bearing gas to the stage'whereit meets the cool aqueous medium containing SO2 in solution, a constant inflow, at relatively constant cool temperature, of water to the stage Where SO2 is absorbed, a relatively constant flow of a part of the SO2 solution from the absorbing stage into the hot SO2-bearing gases, temperature regula-V tion as between vsaid cool solution and said hot gases, such that the cool solution andthe hotV gases are maintained in contact for a suicient period of time not only to release substantially the whole of the SO2 content of the solution but to impar-t to the residual water a temperature sufficient to enable the whole of the SO2 solution vWithdrawn for recovery of SO2 Yto be so elevated in temperature las to effect release of substantially therwhole of the SO2 of said solution.

12. A process such as set forth in claim l in which, after separation of the ultimate SO2 product' of the process, said SO2 is subjected to drying and liquefaction by cooling and ,compression with subsequent lcooling. Y

' FREDRIK W. DE JAHN.

JACOB D. J ENSSEN. 

